Pesticidally active compounds

ABSTRACT

A pesticidally active combination comprising an HPPD-inhibiting herbicide in the form of an agrochemically acceptable salt and an insecticide is disclosed, provided that the HPPD inhibiting herbicide is not a compound of formula (A) wherein R a  is C 1-2  alkyl or chloro; R b  is hydrogen or C 1-4  alkyl; and R c  is C 1-4  alkyl is disclosed.

This application is a 371 of International Application No.PCT/EP2004/012417 filed Nov. 3, 2004, which claims priority to U.S.60/526,053 filed Dec. 1, 2003, and U.S. 60/545,302 filed Feb. 17, 2004,the contents of which are incorporated herein by reference.

The present invention relates to a novel pesticidally active combinationcomprising a herbicidally active ingredient in the form of anagrochemically acceptable salt and one or more insecticidally activeingredients, and optionally one or more additional active ingredients.The invention relates also to a method of controlling unwanted growth incrops of useful plants.

The protection of crops from weeds and other pests that inhibits cropgrowth is a constantly recurring problem in agriculture. To help combatthis problem, researchers in the field of synthetic chemistry haveproduced an extensive variety of chemicals and chemical formulationseffective in the control of such unwanted pests. Chemical pesticides ofmany types have been disclosed in the literature and a large number arein commercial use. Commercial pesticides and some that are still indevelopment are described in The Pesticide Manual 12^(th) Edition,published in 2000 by the British Crop Protection Council.

Agricultural pesticide manufacturers have identified the need forbroad-spectrum pesticidally active products. Single active ingredientformulations rarely meet such broad-spectrum requirements, and thuscombination products, perhaps containing up to four complementarybiologically active ingredients, have been developed. Such products haveseveral additional advantages e.g. elimination of tank mixing; reductionin inventory products; saving in time and money; and a reduction in thenumber of times the crop is sprayed.

One combination considered was a combination of an HPPD inhibitingherbicide with an insecticide. However, when tested, the crop damageseen was considerably increased, compared to that seen followingapplication of the HPPD inhibiting herbicide alone. It was thensurprisingly discovered by the inventors that if an agrochemicallyacceptable salt of the HPPD inhibitor was used a safening effect wasseen and the crop damage caused by the combination was considerablyreduced to an acceptable level.

Accordingly, the present invention provides a pesticidally activecombination comprising an HPPD-inhibiting herbicide in the form of anagrochemically acceptable salt and an insecticide, provided that theHPPD-inhibiting herbicide is not a compound of formula (A)

wherein R^(a) is C₁₋₂ alkyl or chloro; R^(b) is hydrogen or C₁₋₄ alkyl;and R^(c) is C₁₋₄ alkyl.

The HPPD-inhibiting herbicides for use in the present invention aresuitably selected from the group consisting of isoxazoles, triketones,pyrazoles, benzobicyclon and ketospiradox.

Suitably, the isoxazole is a compound of formula (IA)

wherein R is hydrogen or —CO₂R³;

R¹ is C₁₋₄ allyl or C₃₋₆ cycloalkyl optionally substituted by C₁₋₆alkyl;

R² is independently selected from halogen, nitro, cyano, C₁₋₄ alkyl,C₁₋₄ haloalkyl, C₁₋₆ alkoxy, C₁₋₄ haloalkoxy, —(CR⁴R⁵)_(c)S(O)_(b)R⁶,S(O)_(b)R⁶, —OSO₂R⁶ and —N(R⁷)SO₂R⁶; or two groups R², on adjacentcarbon atoms of the phenyl ring may, together with the carbon atoms towhich they are attached, form a 5- or 6-membered saturated orunsaturated heterocyclic ring containing up to three ring heteroatomsselected from nitrogen, oxygen and sulphur, which ring may be optionallysubstituted by one or more groups selected from halogen, nitro, C₁₋₄alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy and —S(O)_(b)R⁶, itbeing understood that a sulphur atom, where present in the ring, may bein the form of a group —SO— or —SO₂—;

R³ is C₁₋₄ alkyl;

R⁴ and R⁵ are independently hydrogen or C₁₋₄ alkyl;

R⁶ is C₁₋₄ alkyl, or phenyl or benzyl, each of phenyl and benzyloptionally bearing from one or five substituents which may be the sameof different selected from the group consisting of halogen, C₁₋₄ alkyl,C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy, nitro and —S(O)_(b)CH₃;

R⁷ is hydrogen or C₁₋₆ alkyl;

a is an integer from one to five;

b is zero, one or two; and

c is one or two (where c is two, the groups (CR⁴R⁵) may be the same ordifferent.

Suitably R is hydrogen; R¹ is cyclopropyl; R² is halogen (preferablychloro), —S(O)_(b)CH₃, or C₁₋₄ haloalkyl (preferably trifluoromethyl);and a is two.

Particularly preferred compounds of formula (IA) include5-cyclopropyl-4-(2-methylsulfonyl-4-trifluoromethyl)benzoylisoxazole(isoxaflutole) and4-(2-chloro-4-methylsulphonyl)benzoyl-5-cyclopropylisoxazole(isoxachlortole).

Suitably, the triketone is a compound of formula (IB),

wherein each R⁸ independently represents (C₁₋₄)allyl or —CO₂R¹¹;

R⁹ represents a halogen atom; a straight- or branched-chain alkyl oralkoxy group containing up to six carbon atoms which is optionallysubstituted by one or more groups —OR¹² or one or more halogen atoms; ora group selected from nitro, cyano, —CO₂R¹³, —S(O)_(f)R¹²,—O(CH₂)_(g)OR¹², —COR¹³, —NR¹³R¹⁴, —SO₂NR¹³R¹⁴, —CONR¹³R¹⁴, —CSNR¹³R¹⁴and —OSO₂R¹⁵;

each R¹⁰ independently represents halo, nitro, cyano, S(O)_(f)R¹⁶,OS(O)_(f)R¹⁶, C₁₋₆ alkyl, C₁₋₆ alkoxy, C₁₋₆ haloalkyl, C₁₋₆ haloalkoxy,carboxy, C₁₋₆ alkylcarbonyloxy, C₁₋₆ alkoxycarbonyl, C₁₋₆ alkylcarbonyl,amino, C₁₋₆ alkylamino, C₁₋₆ dialkylamino having independently thestated number of carbon atoms in each alkyl group, C₁₋₆alkylcarbonylamino, C₁₋₆ alkoxycarbonylamino, C₁₋₆alkylaminocarbonylamino, C₁₋₆ dialkylaminocarbonylamino havingindependently the stated number of carbon atoms in each alkyl group,C₁₋₆ alkoxycarbonyloxy, C₁₋₆ alkylaminocarbonyloxy, C₁₋₆dialkylcarbonyloxy, phenylcarbonyl, substituted phenylcarbonyl,phenylcarbonyloxy, substituted phenylcarbonyloxy, phenylcarbonylamino,substituted phenylcarbonylamino, phenoxy or substituted phenoxy;

R¹¹ is C₁₋₄ alkyl;

R¹² represents a straight- or branched-chain alkyl group containing upto six carbon atoms which is optionally substituted by one or morehalogen atoms;

R¹³ and R¹⁴ each independently represents a hydrogen atom; or astraight- or branched-chain alkyl group containing up to six carbonatoms which is optionally substituted by one or more halogen atoms;

R¹⁵ represents a straight- or branched-chain alkyl, alkenyl or alkynylgroup containing up to six carbon atoms optionally substituted by one ormore halogen atoms; or a cycloalkyl group containing from three to sixcarbon atoms;

R¹⁶ represents a straight- or branched-chain alkyl group containing upto six carbon atoms which is optionally substituted by one or morehalogen atoms;

d is zero or an integer from one to six;

e is zero or an integer from one to four;

f is zero, one or two; and

g is one, two or three.

Suitably, R⁹ is chloro, bromo, nitro, cyano, C₁₋₄ alkyl, —CF₃,—S(O)_(f)R¹², or —OR¹²; each R¹⁰ is independently chloro, bromo, nitro,cyano, C₁₋₄ alkyl, —CF₃, —OR¹², —OS(O)_(f)R¹⁶ or —S(O)_(f)R¹⁶; d is zeroand e is one or two.

Preferred compounds of formula (IB) are2-(2′-nitro-4′-methylsulphonylbenzoyl)-1,3-cyclohexanedione(mesotrione),2-(2′-nitro-4′-methylsulphonyloxybenzoyl)-1,3-cyclohexanedione,2-(2′-chloro-4′-methylsulphonylbenzoyl)-1,3-cyclohexanedione(sulcotrione),4,4-dimethyl-2-(4-methanesulphonyl-2-nitrobenzoyl)-1,3-cyclohexanedione,2-(2-chloro-3-ethoxymethanesulphonylbenzoyl)-5-methyl-1,3-cyclohexanedioneand2-(2-chloro-3-ethoxy-4-ethanesulphonylbenzoyl)-5-methyl-1,3-cyclohexanedione;most preferably is 2-(2′-nitro-4′-methylsulphonylbenzoyl)1,3-cyclohexanedione.

The compounds of formula (IB) may exist in enolic tautomeric forms thatmay give rise to geometric isomers. Furthermore, in certain cases, thevarious substituents may contribute to optical isomerism and/orstereoisomerism. All such tautomeric forms, racemic mixtures and isomersare included within the scope of the present invention.

Alternatively, the triketone is a compound of formula (IC)

wherein V is C₁₋₂ alkylene, which may be mono- or poly-substituted byR²⁹; or, when R²¹ and R²² are other than C₂₋₃ alkylene, W mayadditionally be carbonyl, oxygen or —NR³⁰—;

W is CR³¹ or N(O)_(g);

R²⁰, R²¹, R²² and R²³ are independently hydrogen, C₁₋₄ alkyl, phenyl,C₁₋₄ alkoxy, halogen, hydroxy, cyano, hydroxycarbonyl or C₁₋₄alkoxycarbonyl; or R²¹ and R²² together are C₂₋₃ alkylene, which may bemono- or poly-substituted by R²⁸;

R²⁴ is hydrogen, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₂₋₆ alkenyl, C₂₋₆haloalkenyl, C₁₋₂ alkoxycarbonyl- or phenyl-substituted vinyl, C₂₋₆alkynyl, C₂₋₆ haloalkynyl, trimethylsilyl-, hydroxy-, C₁₋₆ alkoxy-, Calkoxycarbonyl- or phenyl-substituted ethynyl, C₃₋₆ allenyl, C₃₋₆cycloalkyl, halo- or C₁₋₃ alkoxymethyl-substituted C₃₋₆ cycloalkyl, C₁₋₆alkoxy, C₃₋₆ alkenyloxy, C₃₋₆ alkynyloxy, C₁₋₆ haloalkoxy, C₃₋₆haloalkenyloxy, cyano-C₁₋₄ alkoxy, C₁₋₄ alkoxy-C₁₋₄ alkoxy, C₁₋₄alkylthio-C₁₋₄ alkoxy, C₁₋₄ alkylsulfinyl-C₁₋₄ alkoxy, C₁₋₄alkylsulfonyl-C₁₋₄ alkoxy, C₁₋₄ alkoxycarbonyl-C₁₋₄ alkoxy, C₁₋₆alkylthio, C₁₋₆ alkylsulfinyl, C₁₋₆ alkylsulfonyl, C₁₋₆ haloalkylthio,C₁₋₆ haloalkylsulfinyl, C₁₋₆ haloalkylsulfonyl, C₁₋₄ alkoxycarbonyl-C₁₋₄alkylthio, C₁₋₄ alkoxycarbonyl-C₁₋₄ alkylsulfinyl, C₁₋₄alkoxycarbonyl-C₁₋₄ alkylsulfonyl, C₁₋₆ alkylamino, di(C₁₋₆ alkyl)amino,C₁₋₃ alkoxy-C₁₋₃ alkylamino, C₁₋₃ alkoxy-C₁₋₃ alkyl-N(C₁₋₃ alkyl), C₁₋₆alkylaminosulfonyl, di(C₁₋₆ alkyl)aminosulfonyl, C₁₋₄ alkylsulfonyloxy,C₁₋₄ haloalkylsulfonyloxy, C₁₋₄ alkylsulfonylamino, C₁₋₄alkylsulfonyl-N(C₁₋₄ alkyl), cyano, carbamoyl, C₁₋₄ alkoxycarbonyl,formyl, halogen, rhodano, amino, hydroxy-C₁₋₄ alkyl, C₁₋₄ alkoxy-C₁₋₄alkyl, C₁₋₄ alkylthio-C₁₋₄ alkyl, C₁₋₄ alkylsulfinyl-C₁₋₄ alkyl, C₁₋₄alkylsulfonyl-C₁₋₄ alkyl, cyano-C₁₋₄ alkyl, C₁₋₆ alkylcarbonyloxy-C₁₋₄alkyl, C₁₋₄ alkoxycarbonyl-C₁₋₄ alkyl, C₁₋₄ alkoxycarbonyloxy-C₁₋₄alkyl, rhodano-C₁₋₄ alkyl, phenyl-C₁₋₄ alkyl, phenoxy-C₁₋₄ alkyl,benzyloxy-C₁₋₄ alkyl, benzoyloxy-C₁₋₄ alkyl, (2-oxiranyl)-C₁₋₄ alkyl,C₁₋₄ alkylamino-C₁₋₄ alkyl, di(C₁₋₄ alkyl)amino-C₁₋₄ alkyl, C₁₋₁₂alkylthiocarbonyl-C₁₋₄ alkyl or formyl-C₁₋₄ alkyl, or benzylthio,benzylsulfinyl, benzylsulfonyl, benzyloxy, benzyl, phenyl, phenoxy,phenylthio, phenylsulfinyl or phenylsulfonyl, wherein thephenyl-containing groups may themselves be substituted by C₁₋₃ alkyl,C₁₋₃ haloalkyl, C₁₋₃ alkoxy, C₁₋₃ haloalkoxy, halogen, cyano or bynitro; or

R²⁴ is a three- to ten-membered monocyclic or fused bicyclic ringsystem, which may be aromatic, saturated or partially saturated and maycontain from 1 to 4 hetero atoms selected from nitrogen, oxygen andsulfur, wherein the ring system is bonded to the group W-containingaromatic ring by way of a C₁₋₄ alkylene, C₂₋₄ alkenylene or C₂₋₄alkynylene bridge which may be interrupted by oxygen, —N(C₁₋₄ alkyl)-,sulfur, sulfinyl, sulfonyl or by carbonyl, and each ring system maycontain no more than two oxygen atoms and no more than two sulfur atoms,and the ring system may itself be mono-, di- or tri-substituted by C₁₋₆alkyl, C₁₋₆ haloalkyl, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₂₋₆ alkynyl,C₂₋₆ haloalkynyl, C₁₋₆ alkoxy, C₁₋₆ haloalkoxy, C₃₋₆ alkenyloxy, C₃₋₆alkynyloxy, hydroxy, mercapto, C₁₋₆ alkylthio, C₁₋₆ haloalkylthio, C₃₋₆alkenylthio, C₃₋₆ haloalkenylthio, C₃₋₆ alkynylthio, C₁₋₄ alkoxy-C₁₋₃alkylthio, C₁₋₄ alkylcarbonyl-C₁₋₃ alkylthio, C₁₋₄ alkoxycarbonyl-C₁₋₃alkylthio, cyano-C₁₋₃-alkylthio, C₁₋₆ alkylsulfinyl, C₁₋₆haloalkylsulfinyl, C₁₋₆ alkylsulfonyl, C₁₋₆ haloalkylsulfonyl,aminosulfonyl, C₁₋₄ alkylaminosulfonyl, di(C₁₋₄ alkyl)aminosulfonyl,di(C₁₋₄ alkyl)amino, halogen, cyano, nitro, phenyl and/or by benzylthio,wherein phenyl and benzylthio may themselves be substituted on thephenyl ring by C₁₋₃ alkyl, C₁₋₃ haloalkyl, C₁₋₃ alkoxy, C₁₋₃ haloalkoxy,halogen, cyano or by nitro, and wherein substituents on the nitrogen inthe heterocyclic ring are other than halogen; or

R²⁴ is the group —D₁—D₃ or the group —D₂—D₁—D₃;

R²⁵ is hydrogen, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₂₋₆ alkenyl, C₂₋₆haloalkenyl, C₂₋₆ alkynyl, C₂₋₆ haloalkynyl, C₃₋₆ cycloalkyl, C₁₋₆alkoxy, C₁₋₆ haloalkoxy, C₁₋₆ alkylthio, C₁₋₆ alkylsulfinyl, C₁₋₆alkylsulfonyl, C₁₋₆ haloalkylthio, C₁₋₆ haloalkylsulfinyl, C₁₋₆haloalkylsulfonyl, C₁₋₆ alkylsulfonyloxy, hydroxy, mercapto, amino, C₁₋₆alkylamino, di(C₁₋₆ alkyl)amino, C₁₋₄ alkylsulfonylamino, C₁₋₄alkylsulfonyl-N(C₁₋₄ alkyl)-, C₁₋₆ alkylaminosulfonyl, di(C₁₋₆alkyl)aminosulfonyl, cyano, halogen, C₁₋₄ alkoxy-C₁₋₄ alkyl, C₁₋₄alkylthio-C₁₋₄ alkyl, C₁₋₄ alkylsulfinyl-C₁₋₄ alkyl, C₁₋₄alkylsulfonyl-C₁₋₄ alkyl, triazolyl, phenyl, phenylthio, phenylsulfinyl,phenylsulfonyl or phenoxy, wherein the phenyl-containing groups may besubstituted by C₁₋₃ alkyl, C₁₋₃ haloalkyl, C₁₋₃ alkoxy, C₁₋₃ haloalkoxy,halogen, cyano or by nitro;

R²⁶ is hydrogen, C₁₋₆ alkyl, hydroxy, C₁₋₆ alkoxy, C₁₋₆ haloalkoxy, C₃₋₆alkenyloxy, C₃₋₆haloalkenyloxy, C₃₋₆ alkynyloxy, C₁₋₄ alkylcarbonyloxy,C₁₋₄ alkylsulfonyloxy, phenylsulfonyloxy, C₁₋₄ alkylthio, C₁₋₄alkylsulfinyl, C₁₋₄ alkylsulfonyl, C₁₋₄ alkylamino, di(C₁₋₄ alkyl)amino,C₁₋₄ alkoxycarbonyl, C₁₋₄ haloalkyl, formyl, cyano, halogen, phenyl orphenoxy, wherein the phenyl-containing groups may themselves besubstituted by C₁₋₃ alkyl, C₁₋₃ haloalkyl, C₁₋₃ alkoxy, C₁₋₃ haloalkoxy,halogen, cyano or by nitro; or

R²⁶ is a three- to ten-membered monocyclic or, together with R²⁵ or R²⁷,fused bicyclic ring system, which may contain from 1 to 4 hetero atomsselected from nitrogen, oxygen and sulfur, wherein, when the ring systemis not fused, it is bonded to the W-containing aromatic ring, eitherdirectly or by way of a C₁₋₄ alkylene, C₂₋₄ alkenylene or C₂₋₄alkynylene bridge which may be interrupted by oxygen, —N(C₁₋₄ alkyl)-,sulfur, sulfinyl, sulfonyl or by carbonyl, and the ring system maycontain no more than two oxygen atoms and no more than two sulfur atoms,and the ring system may itself be mono-, di- or tri-substituted by C₁₋₆alkyl, C₁₋₆ haloalkyl, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₂₋₆ alkynyl,C₂₋₆ haloalkynyl, C₁₋₆ alkoxy, C₁₋₆ haloalkoxy, C₃₋₆ alkenyloxy, C₃₋₆alkynyloxy, C₁₋₆ alkylthio, C₁₋₆ haloalkylthio, C₃₋₆ alkenylthio, C₃₋₆haloalkenylthio, C₃₋₆ alkynylthio, C₁₋₄ alkoxy-C₁₋₂ alkylthio, C₁₋₄alkylcarbonyl-C₁₋₂ alkylthio, C₁₋₄ alkoxycarbonyl-C₁₋₂ alkylthio,cyano-C₁₋₄ alkylthio, C₁₋₆ alkylsulfinyl, C₁₋₆ haloalkylsulfinyl, C₁₋₆alkylsulfonyl, C₁₋₆ haloalkylsulfonyl, aminosulfonyl, C₁₋₄alkylaminosulfonyl, di(C₁₋₄ alkyl)aminosulfonyl, amino, C₁₋₄ alkylamino, di(C₁₋₄ alkyl)amino, halogen, cyano, nitro, phenyl and by/orbenzylthio, wherein phenyl and benzylthio may themselves be substitutedon the phenyl ring by C₁₋₃ alkyl, C₁₋₃ haloalkyl, C₁₋₃ alkoxy, C₁₋₃haloalkoxy, halogen, cyano or by nitro, and wherein substituents on thenitrogen in the heterocyclic ring are other than halogen;

R²⁷ is hydrogen, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₂₋₆ alkenyl, C₂₋₆haloalkenyl, C₂₋₆ alkynyl, C₂₋₆ haloalkynyl, C₃₋₆ cycloalkyl, C₁₋₆alkoxy, C₁₋₆ haloalkoxy, C₁₋₆ alkylthio, C₁₋₆ alkylsulfinyl, C₁₋₆alkylsulfonyl, C₁₋₆ haloalkylthio, C₁₋₆ haloalkylsulfinyl, C₁₋₆haloalkylsulfonyl, amino, C₁₋₆ alkylamino, di(C₁₋₆ alkyl)amino, C₁₋₄alkylsulfonyl-N(C₁₋₄ alkyl)-, C₁₋₆ alkylaminosulfonyl, di(C₁₋₆alkyl)aminosulfonyl, cyano, halogen, C₁₋₄ alkoxy-C₁₋₄ alkyl, C₁₋₄alkylthio-C₁₋₄ alkyl, C₁₋₄ alkylsulfinyl-C₁₋₄ alkyl, C₁₋₄alkylsulfonyl-C₁₋₄ alkyl, phenyl, phenylthio, phenylsulfinyl,phenylsulfonyl or phenoxy, wherein phenyl groups may themselves besubstituted by C₁₋₃ alkyl, C₁₋₃ haloalkyl, C₁₋₃ alkoxy, C₁₋₃ haloalkoxy,halogen, cyano or by nitro;

R²⁸ and R²⁹ are each independently hydrogen, C₁₋₄ alkyl, phenyl, C₁₋₄alkoxy, halogen, hydroxy, cyano, hydroxycarbonyl or C₁₋₄ alkoxycarbonyl;

R³⁰ is C₁₋₄ alkyl, alkoxycarbonyl or C₁₋₄ alkylcarbonyl;

R³¹ is hydrogen, C₁₋₆ alkyl, hydroxy, C₁₋₆ alkoxy, C₁₋₆ haloalkoxy, C₃₋₆alkenyloxy, C₃₋₆ haloalkenyloxy, C₃₋₆ alkynyloxy, C₁₋₄ alkylcarbonyloxy,C₁₋₄ alkylsulfonyloxy, phenylsulfonyloxy, C₁₋₆ alkylthio, C₁₋₆alkylsulfinyl, C₁₋₆ alkylsulfonyl, C₁₋₆ alkylamino, di(C₁₋₆ alkyl)amino,C₁₋₃ alkoxy-C₁₋₃ alkylamino, C₁₋₃ alkoxy-C₁₋₃ alkyl-N(C₁₋₃ alkyl)-, C₁₋₄alkoxycarbonyl, C₁₋₆ haloalkyl, formyl, cyano, halogen, phenyl orphenoxy, wherein the phenyl-containing groups may themselves besubstituted by C₁₋₃ alkyl, C₁₋₃ haloalkyl, C₁₋₃ alkoxy, C₁₋₃ haloalkoxy,halogen, cyano or by nitro;

or R³¹ is a three- to ten-membered monocyclic or, together with R²⁴ orR²⁵ fused bicyclic ring system, which may be interrupted once or up tothree times by heterocyclic substituents selected from oxygen, sulfur,S(O), SO₂, N(R³²), carbonyl and C(═NOR³³), and wherein, when the ringsystem is not fused, it is bonded to the carbon atom of the substituentW, either directly or by way of a C₁₋₄ alkylene, C₂₋₄ alkenylene or C₂₋₄alkynylene bridge which may be interrupted by oxygen, —N(C₁₋₄ alkyl)-,sulfur, sulfinyl or by sulfonyl, and the ring system may contain no morethan two oxygen atoms and no more than two sulfur atoms, and the ringsystem may itself be mono-, di- or tri-substituted by C₁₋₆ alkyl, C₁₋₆haloalkyl, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₂₋₆ alkynyl, C₂₋₆haloalkynyl, C₁₋₆ alkoxy, C₁₋₆ haloalkoxy, C₃₋₆ alkenyloxy, C₃₋₆alkynyloxy, C₁₋₆ alkylthio, C₁₋₆ haloalkylthio, C₃₋₆ alkenylthio, C₃₋₆haloalkenylthio, C₃₋₆ alkynylthio, C₁₋₄ alkoxy-C₁₋₂ alkylthio, C₁₋₄alkylcarbonyl-C₁₋₂-alkylthio, C₁₋₄ alkoxycarbonyl-C₁₋₂ alkylthio,cyano-C₁₋₄ alkylthio, C₁₋₆ alkylsulfinyl, C₁₋₆ haloalkylsulfinyl, C₁₋₆alkylsulfonyl, C₁₋₆ haloalkylsulfonyl, aminosulfonyl, C₁₋₄alkylaminosulfonyl, di(C₁₋₄ alkyl)aminosulfonyl, di(C₁₋₄ alkyl)amino,halogen, cyano, nitro, phenyl, benzyloxy and/or by benzylthio, andwherein the phenyl-containing groups may themselves be substituted onthe phenyl ring by C₁₋₃ alkyl, C₁₋₃ haloalkyl, C₁₋₃ alkoxy, C₁₋₃haloalkoxy, halogen, cyano or by nitro, and wherein substituents on thenitrogen in the heterocyclic ring are other than halogen;

or R³¹ is the group —D₄—D₆ or the group —D₅—D₄—D₆;

R³² is hydrogen, C₁₋₄ alkyl, C₁₋₄ alkylthio-C₁₋₄ alkylcarbonyl, C₁₋₄alkylsulfinyl-C₁₋₄-alkylcarbonyl, C₁₋₄ alkylsulfonyl-C₁₋₄ alkylcarbonyl,C₁₋₄ alkoxycarbonyl, C₁₋₄ alkylcarbonyl, phenylcarbonyl or phenyl,wherein the phenyl groups may themselves be substituted by C₁₋₄ alkyl,C₁₋₄ haloalkyl, C₁₋₄alkoxy, C₁₋₄ haloalkoxy, C₁₋₄ alkylcarbonyl, C₁₋₄alkoxycarbonyl, C₁₋₄ alkylamino, di(C₁₋₄ alkyl)amino, C₁₋₄ alkylthio,C₁₋₄ alkylsulfinyl, C₁₋₄ alkyl-SO₂, C₁₋₄ alkyl-S(O)₂O, C₁₋₄haloalkylthio, C₁₋₄ haloalkylsulfinyl, C₁₋₄ haloalkyl-SO₂, C₁₋₄haloalkyl-S(O)₂O, C₁₋₄ alkyl-S(O)₂NH, C₁₋₄ alkyl-S(O)₂N(C₁₋₄alkyl)-,halogen, nitro or by cyano;

R³³ is hydrogen, C₁₋₄ alkyl, C₃₋₄ alkenyl, C₃₋₄ alkynyl or benzyl;

h is 0 or 1;

D₁ is oxygen, —O(CO)—, —(CO)O—, —O(CO)O—, —N(C₁₋₄ alkyl)—O—, —O—N(C₁₋₄alkyl)-, thio, sulfinyl, sulfonyl, —SO₂N(C₁₋₄alkyl)-, —N(C₁₋₄alkyl)SO₂—, —N(C₁₋₂ alkoxy-C₁₋₂ alkyl)SO₂— or —N(C₁₋₄ alkyl)-;

D₂ is a C₁₋₆ alkylene, C₃₋₆ alkenylene or C₃₋₆ alkynylene chain, whichmay be mono- or poly-substituted by halogen or by D₇, the unsaturatedbonds of the chain not being bonded directly to the substituent D₁;

D₃ and D₆ are each independently of the other a C₁₋₈ alkyl, C₃₋₆ alkenylor C₃₋₆ alkynyl group, which may be mono- or poly-substituted byhalogen, hydroxy, amino, formyl, nitro, cyano, mercapto, carbamoyl, C₁₋₆alkoxy, C₁₋₆ alkoxycarbonyl, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₂₋₆alkynyl, C₂₋₆ haloalkynyl, C₃₋₆ cycloalkyl, halo-substituted C₃₋₆cycloalkyl, C₃₋₆ alkenyloxy, C₃₋₆ alkynyloxy, C₁₋₆haloalkoxy, C₃₋₆haloalkenyloxy, cyano-C₁₋₆ alkoxy, C₁₋₆ alkoxy-C₁₋₆ alkoxy, C₁₋₆alkoxy-C₁₋₆ alkoxy-C₁₋₆ alkoxy, C₁₋₆ alkylthio-C₁₋₆ alkoxy, C₁₋₆alkylsulfinyl-C₁₋₆ alkoxy, C₁₋₆ alkylsulfonyl-C₁₋₆ alkoxy, C₁₋₆alkoxycarbonyl-C₁₋₆ alkoxy, C₁₋₆ alkoxycarbonyl, C₁₋₆ alkylcarbonyl,C₁₋₆ alkylthio, C₁₋₄ alkylsulfinyl, C₁₋₆ alkylsulfonyl, C₁₋₆haloalkylthio, C₁₋₆ haloalkylsulfinyl, C₁₋₆ haloalkylsulfonyl, oxiranylwhich may itself be substituted by C₁₋₆ alkyl, (3-oxetanyl)-oxy whichmay itself be substituted by C₁₋₆ alkyl, benzyloxy, benzylthio,benzylsulfinyl, benzylsulfonyl, C₁₋₆ alkylamino, di(C₁₋₆ alkyl)amino,C₁₋₄ alkyl-S(O)₂O, di(C₁₋₄ alkyl)aminosulfonyl, rhodano, phenyl,phenoxy, phenylthio, phenylsulfinyl or by phenylsulfonyl, and whereinthe phenyl- or benzyl-containing groups may themselves be substituted byone or more C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₁₋₆ alkoxy, C₁₋₆ haloalkoxy,halogen, cyano, hydroxy or nitro groups; or

D₃ and D₆ are each independently of the other phenyl, which may be mono-or poly-substituted by C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₁₋₆ alkoxy, C₁₋₆haloalkoxy, halogen, cyano, hydroxy or by nitro; or

D₃ and D₆ are each independently of the other C₃₋₆ cycloalkyl, C₁₋₆alkoxy- or C₁₋₆ alkyl-substituted C₃₋₆ cycloalkyl, 3-oxetanyl or C₁₋₆alkyl-substituted 3-oxetanyl; or

D₃ and D₆ are each independently of the other a three- to ten-memberedmonocyclic or fused bicyclic ring system, which may be aromatic,saturated or partially saturated and may contain from 1 to 4 heteroatoms selected from nitrogen, oxygen and sulfur, wherein the ring systemis bonded to the substituent D₁ or D₄ directly or by way of a C₁₋₄alkylene, C₂₋₄ alkenylene, C₂₋₄ alkynylene, —N(C₁₋₄ alkyl)—C₁₋₄alkylene, —S(O)—C₁₋₄ alkylene or —SO₂—C₁₋₄ alkylene group, and each ringsystem may contain no more than two oxygen atoms and no more than twosulfur atoms, and the ring system may itself be mono-, di- ortri-substituted by C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₂₋₆ alkenyl, C₂₋₆haloalkenyl, C₂₋₆ alkynyl, C₂₋₆ haloalkynyl, C₁₋₆ alkoxy, hydroxy,C₁₋₆-haloalkoxy, C₃₋₆ alkenyloxy, C₃₋₆ alkynyloxy, mercapto, C₁₋₆alkylthio, C₁₋₆ haloalkylthio, C₃₋₆ alkenylthio, C₃₋₆ haloalkenylthio,C₃₋₆ alkynylthio, C₁₋₃ alkoxy-C₁₋₃ alkylthio, C₁₋₄ alkylcarbonyl-C₁₋₂alkylthio, C₁₋₄ alkoxycarbonyl-C₁₋₂ alkylthio, cyano-C₁₋₃ alkylthio,C₁₋₆ alkylsulfinyl, C₁₋₆ haloalkylsulfinyl, C₁₋₆ alkylsulfonyl, C₁₋₆haloalkylsulfonyl, aminosulfonyl, C₁₋₂alkylaminosulfonyl, di(C₁₋₂alkyl)aminosulfonyl, di(C₁₋₄alkyl)amino, C₁₋₆ carbonylamino, halogen,cyano, nitro, phenyl, benzyloxy and/or by benzylthio, wherein the phenylgroups may themselves be substituted on the phenyl ring by C₁₋₃ alkyl,C₁₋₃ haloalkyl, C₁₋₃ alkoxy, C₁₋₃ haloalkoxy, halogen, cyano or bynitro, and wherein the substituents on the nitrogen in the heterocyclicring are other than halogen;

D₄ is oxygen, —O(CO)—, —(CO)O—, —O(CO)O—, —N(C₁₋₄ alkyl)-O—, —O—N(C₁₋₄alkyl)-, sulfur, sulfinyl, sulfonyl, —SO₂N(C₁₋₄ alkyl)-, —N(C₁₋₄alkyl)SO₂—, —N(C₁₋₂ alkoxy-C₁₋₂ alkyl)SO₂— or —N(C₁₋₄ alkyl)-;

D₅ is a C₁₋₆ alkylene, C₃₋₆ alkenylene or C₃₋₆ alkynylene chain, whichmay be mono- or poly-substituted by halogen or by D₈, the unsaturatedbonds of the chain not being bonded directly to the substituent D₄;

D₇ and D₈ are each independently of the other hydroxy, C₁₋₆ alkoxy,(C₃₋₆ cycloalkyl)oxy, C₁₋₆ alkoxy-C₁₋₆ alkoxy, C₁₋₆ alkoxy-C₁₋₆alkoxy-C₁₋₆ alkoxy or C₁₋₆ alkylsulfonyloxy;

and agronomically acceptable salts/N-oxides/isomers/enantiomers of suchcompounds.

Alternatively, the triketone may be present in an enolic form and is acompound of formula (ID)

wherein R³⁴ and R³⁵ are both hydrogen or together form an ethylenebridge.

The compound of formula (ID) wherein both R³⁴ and R³⁵ are hydrogen ishereinafter referred to as compound (IDa), and the compound of formula(I) wherein R³⁴ and R³⁵ together form an ethylene bridge is hereinafterreferred to as compound (IDb).

Suitably, the pyrazole is a compound of formula (IE)

wherein R³⁶, R³⁷, R³⁸ and R³⁹ are each independently selected fromhydrogen, halo or C₁₋₄ alkyl;

X is —SO₂— or —CH₂CO—;

j is 2 or 3; and

k is zero or 1.

Suitably R³⁶, R³⁷, R³⁸ and R³⁹ are each independently hydrogen, chloroor methyl.

Preferred compounds of formula (IE) include2-[[4-(2,4-dichloro-3-methylbenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl]oxy]-1-(4-methylphenyl)ethanone(benzofenap),(2,4-dichlorophenyl)[1,3-dimethyl-5-[[(4-methylphenyl)sulfonyl]oxy]-1H-pyrazol-4-yl]methanone(pyrazolynate) and2-[[4-(2,4-dichlorobenzoyl)-1,3-dimethyl-1H-pyrazol-5-yl]oxy]-1-phenylethanone(pyrazoxyfen).

Benzobicyclon is a compound of formula (IF)

Ketospiradox is a compound of formula (IG)

Agriculturally acceptable salts for use in the present invention includesalts the cations or anions of which are known and accepted in the artfor the formation of salts for agricultural or horticultural use. Usefulsalts for practice of the invention may be formed from compounds offormulae (IA) to (IG) using amines, alkali metal bases, alkaline earthmetal bases, quaternary ammonium bases, and metal chelates. Alsoincluded are metal chelates of compounds of formulae (IA) to (IG),particularly compounds of formula (IB), including salts of di- andtrivalent transition metal ions such as Cu⁺², Zn⁺², Co⁺², Ni⁺², Ca⁺²,Al⁺³, Ti⁺³, Fe⁺³, Fe⁺³, Ba⁺², Cs⁺², and also [CH₃(CH₂)₇]3N.

Examples of suitable amines for ammonium salt formation that come intoconsideration are ammonia as well as primary, secondary and tertiaryC₁₋₁₈ alkylamines, C₁₋₄ hydroxyalkylamines and C₂₋₄ alkoxyalkylamines,for example methylamine, ethylamine, n-propylamine, isopropylamine, thefour butylamine isomers, n-amylamine, isoamylamine, hexylamine,heptylamine, octylamine, nonylamine, decylamine, pentadecylamine,hexadecylamine, heptadecylamine, octadecylamine, methyl-ethylamine,methyl-isopropylamine, methyl-hexylamine, methyl-nonylamine,methyl-pentadecylamine, methyl-octadecylamine, ethyl-butylamine,ethyl-heptylamine, ethyl-octylamine, hexyl-heptylamine,hexyl-octylamine, dimethylamine, diethylamine, di-n-propylamine,diisopropylamine, di-n-butylamine, di-n-amylamine, diisoamylamine,dihexylamine, diheptylamine, dioctylamine, ethanolamine,n-propanolamine, isopropanolamine, N,N-diethanolamine,N-ethylpropanolamine, N-butylethanolamine, allylamine,n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine,dibutenyl-2-amine, n-hexenyl-2-amine, propylenediamine, trimethylamine,triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine,triisobutylamine, tri-sec-butylamine, tri-n-amylamine, methoxyethylamineand ethoxyethylamine; heterocyclic amines, for example pyridine,quinoline, isoquinoline, morpholine, piperidine, pyrrolidine, indoline,quinuclidine and azepine; primary aryl amines for example anilines,methoxyanilines, ethoxyanilines, o-, m- and p-toluidines,phenylenediamines, benzidines, naphthylamines and o-, m- andp-chloroanilines; but especially triethylamine, isopropylamine anddiisopropylamine.

The selection of a particular metal ion to form a metal chelate compoundof a compound of formulae (IA) to (IG); particularly (IB), will dependupon the dione compound to be chelated. For example, metal chelates ofcompounds of formula (IB) and their preparation are described, interalia, in PCT Publication No. WO97/27748. Metal chelates of compounds offormula (IB) have the general structure:

wherein R⁸, R⁹, R¹⁰, d and e are as hereinbefore defined, and

wherein M represents a di- or trivalent metal ion such as Cu⁺², Zn⁺²,Co⁺², Ni⁺², Ca⁺², Al⁺³, Ti⁺³, Fe⁺², Fe⁺³, Ba⁺², Cs⁺² and also[CH₃(CH₂)₇]₃N. The preferred metal ions are divalent transition metalions, particularly Cu⁺², Co⁺², Ni⁺², and Zn⁺²; with Cu⁺² beingespecially preferred. Any appropriate salt which would be a source of adi- or trivalent metal ion may be used to form the metal chelate of thedione compound in accordance with this invention. Particularly suitablesalts include: chlorides, sulphates, nitrates, carbonates, phosphatesand acetates.

Insecticides suitable for use in the present invention includeAbamectin, Acephate, Acetamiprid, Acrinathrin, Acrylonitrile, Alanycarb,Aldicarb, Aldoxycarb, Aldrin, Allethrin (1R-isomers), Allyxycarb,Alpha-cypermethrin, Phosphine (Aluminium Phosphide), Amidithion,Aminocarb, Amiton, Amitraz, Anabasine, Athidathion, Azadirachtin,Azamethiphos, Azinphos-ethyl, Azinphos-methyl, Azothoate, Bacillussphaericus, Bacillus thuringiensis, Bacillus thuringiensis deltaendotoxins, Barium polysulfide, Bendiocarb, Benfuracarb, Bensultap,Benzoximate, Beta-cyfluthrin, Beta-cypermethrin, Bifenthrin,Bioallethrin, Bioallethrin S-cyclopentenyl isomer, Biopemiethrin,Bioresmethrin, Bistrifluron, Borax, Bromfenvinfos, Bromophos,Bromophos-ethyl, Bufencarb, Buprofezin, Butacarb, Butathiofos,Butocarboxim, Butonate, Butoxycarboxim, Cadusafos, Hydrogen cyanide,Calcium polysulfide, Camphechlor, Carbanolate, Carbaryl, Carbofuran,Carbon disulfide, Carbon tetrachloride, Carbophenothion, Carbosulfan,Cartap, Chlorbicyclen, Chlordane, Chlordecone, Chlordimeform,Chlorethoxyfos, Chlorfenapyr, Chlorfenvinphos, Chlorfluazuron,Chlormephos, Chloropicrin, Chlorphoxim, Chlorprazophos, Chlorpyrifos,Chlorpyrifos-methyl, Chlorthiophos, Chromafenozide, Clothianidin,Coumaphos, Coumithoate, Crotoxyphos, Crufomate, Cryolite, Cyanofenphos,Cyanophos, Cyanthoate, Cycloprothrin, Cyfluthrin, Cyhalothrin,Cypermethrin, Alpha-cypermethrin, Beta-Cypermethrin, Theta-cypermethrin,Zeta-cypermethrin, Cyphenothrin, Cyromazine, Dazomet, Bromo-DDT, DDT,pp′-DDT, Decarbofuran, Deltamethrin, Demephion, Demephion-O,Demephion-S, Demeton, Demeton-O, Demeton-S, Demeton-methyl,Demeton-O-methyl, Demeton-S-methyl, Demeton-S-methylsulphon,Diafenthiuron, Dialifos, Diazinon, Dicapthon, Dichlofenthion,Dichlorvos, Dicrotophos, Dicyclanil, Dieldrin, Diflubenzuron, Dimefox,Dimethoate, Dimethrin, Dimethylvinphos, Dimetilan, Dinex, Dinotefuran,Diofenolan, Dioxabenzofos, Dioxacarb, Dioxathion, Disulfoton,Dithicrofos, DNOC, Emamectin, EMPC, Empenthrin, Endosulfan, Endothion,EPN, Epofenonane, Esfenvalerate, Ethiofencarb, Ethion, Ethoate-methyl,Ethoprophos, Ethylene dibromide, Ethylene dichloride, Etofenprox,Etrimfos, Famphur, Fenchlorphos, Fenethacarb, Fenfluthrin, Fenitrothion,Fenobucarb, Fenoxycarb, Fenpirithrin, Fenpropathrin, Fensulfothion,Fenthion, Fenvalerate, Fipronil, Flonicamid, Flucofuron, Flucycloxuron,Flucythrinate, Flucythrinate, Flucythrinate, Flufenprox, Flumethrin,Fluvalinate, Fonofos, Formetanate, Formothion, Fosmethilan, Fospirate,Fosthiazate, Fosthietan, Furathiocarb, Furethrin, gamma-HCH, GY-81,Halofenozide, Heptachlor, Heptenophos, Hexaflumuron, Hydramethylnon,Hydrogen cyanide, Hydroprene, Imidacloprid, Imiprothrin, Indoxacarb,IPSP, Isazofos, Isobenzan, Isodrin, Isofenphos, Isoprocarb, IsopropylO-(methoxyaminothiophosphoryl)salicylat, Isothioate, Isoxathion,Jodfenphos, Kelevan, Kinoprene, Lambda-cyhalothrin, Lirimfos, Lufenuron,Lythidathion, Phosphine, Malathion, Mazidox, Mecarbam, Mecarphon,Menazon, Mephosfolan, Mercurous chloride, Mesulfenfos, Metam,Methacrifos, Methamidophos, Methidathion, Methiocarb, Methocrotophos,Methomyl, Methoprene, Methothrin, Methoxychlor, Methoxyfenozide, Methylbromide, Methyl isothiocyanate, Metolcarb, Metoxadiazone, Mevinphos,Mexacarbate, Milbemectin, Mipafox, Mirex, Monocrotophos, Morphothion,Naled, Nicotine, Nifluridide, Nitenpyram, Nithiazine, Nitrilacarb,Novaluron, Ölsäure, Omethoate, Oxamyl, Oxydemeton-methyl, Oxydeprofos,Oxydisulfoton, Parathion, Parathion-methyl, Pentachlorophenol,Permethrin, Petroleum Öl, Phenkapton, Phenothrin, Phenthoate, Phorate,Phosalone, Phosfolan, Phosmet, Phosnichlor, Phosphamidon, Phoxim,Phoxim-methyl, Pirimetaphos, Pirimicarb, Pirimiphos-ethyl,Pirimiphos-methyl, Prallethirin, Primidophos, Profenofos, Promacyl,Promecarb, Propaphos, Propetamphos, Propoxur, Prothiofos, Prothoate,Pymetrozine, Pyraclofos, Pyrazophos, Pyresmethrin, Pyrethrins,Pyridaben, Pyridaphenthion, Pyrimidifen, Pyrimitate, Pyriproxyfen,Quinalphos, Quinalphos-methyl, Quinothion, Resmethrin, Rotenone, RU15525, Sabadilla, Schradan, Silafluofen, Sodium fluoride, Sodiumhexafluorosilicate, Pentachlorophenol, Sophamide, Spinosad, Sulcofuron,Sulfluramid, Sulfotep, Sulfuryl fluoride, Sulprofos, Tau-fluvalinate,Tazimcarb, TDE, Tebufenozide, Tebupirimfos, Teflubenzuron, Tefluthrin,Temephos, TEPP, Terallethrin, Terbufos, Tetrachlorvinphos, Tetramethrin,Tetramethrin [(1R)-isomers], Thiacloprid, Thiamethoxam, Thicrofos,Thiocarboxime, Thiocyclam, Thiodicarb, Thiofanox, Thiometon,Thiosultap-sodium, Tolfenpyrad, Tralomethrin, Transfluthrin,Transpermethrin, Triazamate, Triazofos, Trichlorfon, Trichloronat,Tridec-4-enyl acetate, Trifenofos, Triflumuron, Trimethacarb, Triprene,Vamidothion, XMC, Xylylcarb, Spirodiclofen, Acetoprole, Fluacrypyrim,Pyridalyl, Noviflumuron, Flufenerim, Amidoflumet, Ethiprole,Acequinocyl, Etoxazole, Bifenazate, Spiromesifen and ZXI 8901. The aboveinsecticides are described in the Pesticide Manual, 12^(th) ed., BritishCrop Protection Council 2000.

In a preferred embodiment of the invention, the insecticide is notlambda-cyhalothrin when the HPPD-inhibiting herbicide is2-(2′-nitro-4′-methylsulphonylbenzoyl)-1,3-cyclohexanedione(mesotrione).

Particularly preferred combinations of HPPD-inhibiting herbicide saltand insecticide include agrochemically acceptable salts of isoxaflutole,isoxachlortole, mesotrione, sulcotrione, Compound (IDa), Compound (IDb),benzofenap, pyrazolynate, pyrazoxyfen, Benzobicyclon or Ketospiradoxwith chlorpyrifos, chlorpyrifos-methyl, terbufos, tefluthrin orthiamethoxam.

In a further preferred embodiment of the invention, if the insecticideis terbufos or chlorpyrifos and the HPPD-inhibiting herbicide is2-(2′-nitro-4′-methylsulphonylbenzoyl)-1,3-cyclohexanedione(mesotrione), the herbicide is suitably given post-emergence.

The pesticidally active combination according to the invention can beused against a large number of agronomically important weeds, such asStellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis,Lolium, Solanum, Phaseolus, Echinochloa, Scirpus, Monochoria,Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus,Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea,Chrysanthemum, Galium, Viola and Veronica. The combination according tothe invention is suitable for all methods of application conventionallyused in agriculture, e.g. pre-emergence application, post-emergenceapplication and seed dressing. Suitably, at least the HPPD-inhibitingherbicide is applied post-emergence, in particular when applied with aorganophosphate or carbamate insecticide. The combination according tothe invention is suitable especially for controlling weeds in crops ofuseful plants, such as cereals, rape, sugar beet, sugar cane, plantationcrops, rice, maize and soybeans, and also for non-selective weedcontrol. “Crops” are to be understood also to include those crops whichhave been made tolerant to herbicides or classes of herbicides as aresult of conventional methods of breeding or genetic engineering. Thecomponents used in the combination of the invention can be applied in avariety of ways known to those skilled in the art, at variousconcentrations. The rate at which the herbicidal components are appliedwill depend upon the particular type of weed to be controlled, thedegree of control required, and the timing and method of application. Ingeneral, the components can be applied at an application rate of betweenabout 10 g a.i./hectare (g/ha) and about 7500 g a.i./ha, based on thetotal amount of active ingredient. An application rate of between about50 g a.i/ha and 5000 g a.i./ha is preferred. Suitably, theHPPD-inhibiting herbicide salt is applied at a rate of 1-500 g a.i./ha,preferably 50-250 g a.i/ha; and the insecticide compound is applied at arate of 5-2500 g a.i/ha, preferably 50-2000 g a.i./ha. In an especiallypreferred embodiment of this invention, the components are administeredin relative amounts sufficient to provide an application rate of atleast 2000 g a.i./ha, of which the HPPD-inhibiting herbicide saltprovides at least 100 g/ha. Generally the mixing ratios (by weight) ofHPPD and Insecticide compound are from 1:2000 to 2000:1; preferably1:200 to 200:1.

The components used in the combination of the invention may beadministered simultaneously or sequentially. If administeredsequentially, the components may be administered in any order in asuitable timescale, for example the insecticide may be administered atplanting and the HPPD-inhibiting herbicide salt administeredpost-emergent.

If the components are administered simultaneously, they may beadministered separately or as a tank mix or as a pre-formulated mixtureof all the components or as a pre-formulated mixture of some of thecomponents tank mixed with the remaining components.

Therefore, a yet further aspect of the invention provides a pesticidallyactive pre-mix composition comprising a HPPD-inhibiting herbicide in theform of an agrochemically acceptable salt and an insecticide, providedthat the HPPD-inhibiting herbicide is not a compound of formula (A)

wherein R^(a) is C₁₋₂ alkyl or chloro; R^(b) is hydrogen or C₁₋₄ alkyl;and R^(c) is C₁₋₄ alkyl.

A yet further aspect of the invention provides a pesticidally activecombination or pre-mix composition comprising an HPPD inhibitingherbicide in the form of a salt and an insecticide as hereinbeforedefined, in combination with one or more additional active ingredients.Such additional active ingredients may be other herbicides, fungicides,insecticides, or the like or safeners. In particular, the one or moreadditional active ingredients are herbicides and/or safeners. Examplesof suitable additional herbicides and/or safeners for use in the presentinvention include atrazine, terbuthylazine, metolachlor, s-metolachlor,benoxacor, furilazole, dichlormid, flurazole acetochlor, p-dimethenamid,glyphosate, cloquintocet, fluxofenim, nicosulfuron, rimsulfuron,foramsulfuron, isoxadifene, prosulfuron, primisulfuron, dicamba,trifloxysulfuron and the like. The pesticidal combination may contain,in addition to the main two components, an additional one, two, three,four or more components of the additional herbicides and/or safenerslisted above.

The present invention is also directed to methods of controllingundesired plant growth in crops of useful plants, said method comprisingthe application of a pesticidally active amount of the combination orpre-mix composition of the invention to the cultivated plant or itslocus. The method is especially useful where the cultivated plant ismaize or a cereal.

The present invention will now be further described with reference tothe following examples.

EXAMPLE 1

Field tests were conducted in the following way: Corn was seeded withstandard sowing implements and grown under natural conditions until the2-3 leaf stage of corn was reached. Corn with or without insecticidetreatments applied at seeding was grown at the same time. At 2-3 leafstage, the herbicides only or in combination with the insecticide, ifthe insecticide has not been applied at seeding, was applied broadcastfoliar over the top. At highest phytotoxicity levels for corn at fivedays after application and at maximal weed control levels at 16 daysafter application, the trial was evaluated. The results are shown in thefollowing Table I:

TABLE I Crop/Variety Sweet Corn Weed/ Corn ‘Jubilee Amaranthus ‘NK58D1SS retroflexus Rating Data Type Weed Phytotox. Phytotox. Control RatingUnit Scale % % % Evaluation @ Days after All post applications with:last application COC @ 1% V/V + 5 5 16 Appln. UAN @ 2.5% V/V Rate ScaleMin-Max Trt Timing Treatment/Product a.i. rate Unit 0-100 0-100 0-100 1Check untreated 0 0 0 2 Post Mesotrione 105 GA/ 3.8 16.3 90 Ha 3 PostMesotrione-Cu + s- 105(a.e) + 1053 + 52.5 GA/ 0 0 71.3 metolachlor +benoxacor Ha 4 Post Mesotrione-Cu + s- 105(a.e) + 1053 + 394 + 52.5 GA/2 1.3 95 metolachlor + atrazine + benoxacor Ha 5 Post Mesotrione-Cu105(a.e.) GA/ 0 0 87.5 Ha 6 Post Mesotrione 210 GA/ 8.8 15 95 Ha 7 PostMesotrione-Cu + s- 210(a.e) + 2105 + 105 GA/ 0 0 88.8 metolachlor +benoxacor Ha 8 Post Mesotrione-Cu + s- 210(a.e) + 2100 + 788 + 105 GA/6.3 1.3 95 metolachlor + atrazine + benoxacor Ha 9 Post Mesotrione-Cu210(a.e) GA/ 0 0 95 Ha 10 In furrow Chlorpyrifos 11.2 GA/ 0 0 0 atseeding 100 Row M 11 In furrow Chlorpyrifos 11.2 GA/ 6.3 30 88.8 atseeding 100 Row M Followed Mesotrione 105 GA/ post Ha 12 In furrowChlorpyrifos 11.2 GA/ 0 0 71.3 at seeding 100 Row M FollowedMesotrione-Cu + s- 105(a.e) + 1053 + 52.5 GA/ post metolachlor +benoxacor Ha 13 In furrow Chlorpyrifos 11.2 GA/ 1.3 1.3 95 at seeding100 Row M Followed Mesotrione-Cu + s- 105(a.e) + 1053 + 394 + 52.5 GA/post metolachlor + atrazine + benoxacor Ha 14 In furrow Chlorpyrifos11.2 GA/ 0 0 82.5 at seeding 100 Row M Followed Mesotrione-Cu 105(a.e)GA/ post Ha 15 In furrow Chlorpyrifos 11.2 GA/ 15 28.8 95 at seeding 100Row M Followed Mesotrione 210 GA/ post Ha 16 In furrow Chlorpyrifos 11.2GA/ 1.3 0 93.8 at seeding 100 Row M Followed Mesotrione-Cu + s-210(a.e) + 2105 + 105 GA/ post metolachlor + benoxacor Ha 17 In furrowChlorpyrifos 11.2 GA/ 10 5 95 at seeding 100 Row M FollowedMesotrione-Cu + s- 210(a.e) + 2100 + 788 + 105 GA/ post metolachlor +atrazine + benoxacor Ha 18 In furrow Chlorpyrifos 11.2 GA/ 0.8 0 95 atseeding 100 Row M Followed Mesotrione-Cu 210(a.e) GA/ post Ha 19 Infurrow Terbufos 11.2 GA/ 0 0 0 at seeding 100 Row M 20 In furrowTerbufos 11.2 GA/ 13.8 43.8 88.8 at seeding 100 Row M FollowedMesotrione 105 GA/ post Ha 21 In furrow Terbufos 11.2 GA/ 0 0 73.8 atseeding 100 Row M Followed Mesotrione-Cu + s- 105(a.e) + 1053 + 52.5 GA/post metolachlor + benoxacor Ha 22 In furrow Terbufos 11.2 GA/ 2.5 093.8 at seeding 100 Row M Followed Mesotrione-Cu + s- 105(a.e) + 1053 +394 + 52.5 GA/ post metolachlor + atrazine + benoxacor Ha 23 In furrowTerbufos 11.2 GA/ 0 0 83.8 at seeding 100 Row M Followed Mesotrione-Cu105(a.e) GA/ post Ha 24 In furrow Terbufos 11.2 GA/ 26.3 43.8 95 atseeding 100 Row M Followed Mesotrione 210 GA/ post Ha 25 In furrowTerbufos 11.2 GA/ 2 0 76.3 at seeding 100 Row M Followed Mesotrione-Cu +s- 210(a.e) + 2105 + 105 GA/ post metolachlor + benoxacor Ha 26 Infurrow Terbufos 11.2 GA/ 7.5 7.5 95 at seeding 100 Row M FollowedMesotrione-Cu + s- 210(a.e) + 2100 + 788 + 105 GA/ post metolachlor +atrazine + benoxacor Ha 27 In furrow Terbufos 11.2 GA/ 1.3 0 95 atseeding 100 Row M Followed Mesotrione-Cu 210(a.e) GA/ post Ha 28 PostChlorpyrifos 1120 GA/ 0 0 0 Ha 29 Post tank Chlorpyrifos 1120 GA/ 460361.3 95 mix/foliar Ha Mesotrione 105 GA/ Ha 30 Post Chlorpyrifos 1120GA/ 3.8 2.5 81.3 tankmix/ Ha foliar Mesotrione-Cu + s- 105(a.e) + 1053 +52.5 GA/ metolachlor + benoxacor Ha 31 Post Chlorpyrifos 1120 GA/ 7 8.893.8 tankmix/ Ha foliar Mesotrione-Cu + s- 105(a.e) + 1050 + 394 + 52.5GA/ metolachlor + atrazine + benoxacor Ha 32 Post Chlorpyrifos 1120 GA/5 8.8 91.3 tankmix/ Ha foliar Mesotrione-Cu 105(a.e) GA/ Ha 33 PostChlorpyrifos 1120 GA/ 70 75 92.5 tankmix/ Ha foliar Mesotrione 210 GA/Ha 34 Post Chlorpyrifos 1120 GA/ 8.8 3.3 93.8 tankmix/ Ha foliarMesotrione-Cu + s- 210(a.e) + 2105 + 105 GA/ metolachlor + benoxacor Ha35 Post Chlorpyrifos 1120 GA/ 20 10 95 tankmix/ Ha foliarMesotrione-Cu + s- 210(a.e) + 2100 + 788 + 105 GA/ metolachlor +atrazine + benoxacor Ha 36 Post Chlorpyrifos 1120 GA/ 8.8 12.5 95tankmix/ Ha foliar Mesotrione-Cu 210(a.e) GA/ Ha

EXAMPLE 2 Insecticide Pre-Plant Incorporated Followed by PostApplication of the Herbicide

Prior to the planting of corn and weed, the substrate was filled intoplastic pots and the different insecticides were applied with glasshousespray equipment on bare soil at rates indicated in the results table.After the insecticide application, the substrate in the pots was mixedup in order to get an even distribution of the insecticide throughoutthe pot Crop and weed were planted following this procedure and grownunder standard glasshouse conditions allowing optimal plant growth until2-3 leaf stage. Then the herbicides were applied according to the ratesindicated in the results table post emergent foliar over the topincluding standard adjuvants. The plants were visually evaluated on ascale of 0-100% wherein 0% indicated no phytotoxicity and 100% indicatedfull control or death. 0-15% indicates acceptable crop tolerance,85-100% acceptable weed control. The evaluation was done at the timewhen maximal phytotoxicity or activity occurred. The results are shownin Table 2.

TABLE 2 Crop/Variety Weed/ Corn Solanum Cecilia Nigrum Rating Data TypeWeed Phytotox. Control Rating Unit Scale % % Evaluation @ All post Daysafter last applications with: application COC @ 1% V/V + 20 43 Appln.UAN @ 2.5% V/V a.i. rate/ Scale Min-Max Trt Timing Treatment/ProductGA/Ha 0-100 0-100 1 Post Mesotrione 400 0 0 200 0 100 100 5 98 2 PostMesotrione-Cu 400 0 100 200 0 95 100 5 95 3 Pre-plantChlorpyrifos-methyl 1000 incorporated Post Mesotrione 400 30 100 200 20100 100 20 98 4 Pre-plant Chlorpyrifos-methyl 1000 incorporated PostMesotrione-Cu 400 0 100 200 0 100 100 0 100 5 Pre-plant Terbufos 1000incorporated Post Mesotrione 400 30 100 200 30 100 100 20 100 6Pre-plant Terbufos 1000 incorporated Post Mesotrione-Cu 400 0 100 200 0100 100 0 98 7 Pre-plant Tefluthrin 1000 incorporated Post Mesotrione400 30 100 200 30 100 100 25 98 8 Pre-plant Tefluthrin 1000 incorporatedPost Mesotrione-Cu 400 0 100 200 0 100 100 0 100 9 Pre-plantThiamethoxam 1000 incorporated Post Mesotrione 400 30 100 200 30 95 10020 100 10 Pre-plant Thiamethoxam 1000 incorporated Post Mesotrione-Cu400 0 100 200 0 100 100 0 100 11 Post (ICb) 200 25 98 100 5 98 50 5 9812 Post (ICb)-Cu 200 0 85 100 0 90 50 5 85 13 Pre-plantChlorpyrifos-methyl 1000 incorporated Post (ICb) 200 40 100 100 30 10050 20 100 14 Pre-plant Chlorpyrifos-methyl 1000 incorporated Post(ICb)-Cu 200 5 100 100 5 98 50 0 98 15 Pre-plant Terbufos 1000incorporated Post (ICb) 200 40 100 100 40 100 50 20 95 16 Pre-plantTerbufos 1000 incorporated Post (ICb)-Cu 200 10 90 100 5 100 50 5 100 17Pre-plant Tefluthrin 1000 incorporated Post (ICb) 200 40 100 100 40 10050 20 100 18 Pre-plant Tefluthrin 1000 incorporated Post (ICb)-Cu 200 0100 100 0 100 50 10 95 19 Pre-plant Thiamethoxam 1000 incorporated Post(ICb) 200 30 100 100 30 100 50 20 100 20 Pre-plant Thiamethoxam 1000incorporated Post (ICb)-Cu 200 5 100 100 0 90 50 0 90

EXAMPLE 3 Insecticide and Herbicide Applied Tank-Mixed Post Emergent

Prior to the planting of corn and weed, the substrate was filled intoplastic pots. Crop and weed were planted following this procedure andgrown under standard glasshouse conditions allowing optimal plant growthuntil 2-3 leaf stage. Then the herbicides were applied according therates indicated in the results table post emergent foliar over the topincluding standard adjuvants. The plants were visually evaluated on ascale of 0-100% wherein 0% indicated no phytotoxicity and 100% indicatedfull control or death. 0-15% indicates acceptable crop tolerance,85-100% acceptable weed control. The evaluation was done at the timewhen maximal phytotoxicity or activity occurred. The results are shownin Table 3.

TABLE 3 Crop/Variety Corn Weed/ Sweet Solanum honeycomb Nigrum RatingData Type Weed Phytotox. Control Rating Unit Scale % % Evaluation @ Daysafter last application 8 34 Appln. a.i. rate/ Scale Min-Max Trt TimingTreatment/Product GA/Ha 0-100 0-100 1 Post Mesotrione 400 20 100 200 20100 100 10 100 2 Post Mesotrione-Cu 400 0 100 200 0 100 100 0 95 3 PostChlorpyrifos-methyl 1000 Mesotrione 400 100 100 200 90 100 100 85 100 4Post Chlorpyrifos-methyl 1000 Mesotrione-Cu 400 10 100 200 0 95 100 0100 5 Post Terbufos 1000 Mesotrione 400 50 100 200 30 100 100 15 100 6Post Terbufos 1000 Mesotrione-Cu 400 0 100 200 0 100 100 0 100 7 PostTefluthrin 100 Mesotrione 400 30 100 200 20 100 100 20 100 8 PostTefluthrin 100 Mesotrione-Cu 400 0 100 200 0 100 100 0 100 9 PostThiamethoxam 70 Mesotrione 400 25 100 200 20 100 100 10 100 10 PostThiamethoxam 70 Mesotrione-Cu 400 0 100 200 0 100 100 0 100

1. A pesticidally active combination comprising mesotrione copper saltand an insecticide selected from the group consisting ofchlorpyrifos-methyl, terbufos, tefluthrin and thiamethoxam.
 2. Apesticidally active combination according to claim 1, wherein theagrochemically acceptable salt is formed using metal chelates.
 3. Apesticidally active combination according to claim 1, which comprisesone or more additional active ingredients.
 4. A pesticidally activecombination according to claim 3, wherein the one or more additionalactive ingredients are herbicides and/or safeners.
 5. A pesticidallyactive combination according to claim 3, wherein the one or moreadditional active ingredients are selected from the group consisting ofatrazine, terbuthylazine, metolachlor, s-metolachlor, benoxacor,furilazole, dichlormid, flurazole acetochlor, p-dimethenamid,glyphosate, cloquintocet, fluxofenim, nicosulfuron, rimsulfuron,foramsulfuron, isoxadifene, prosulfuron, primisulfuron, dicamba,trifloxysulfuron.
 6. A method of controlling undesired plant growth incrops of useful plants, said method comprising the application of thepesticidally active combination of claim
 1. 7. A pesticidally activepre-mix composition comprising mesotrione copper salt and an insecticideselected from the group consisting of chlorpyrifos-methyl, terbufos,tefluthrin and thiamethoxam.